Methanol crossover through the Nation membrane is a perennial problem in the operation of direct methanol fuel cells (DMFCs) and therefore justifies the search fora Nafion substitute. This study reports anew methanol-blocking polymer matrix which consists of a methanol barrier phase and an embedded proton source. A three-component polymer blend (TCPB) of poly(4-vinylphenol-co-methyl metbacrylate), poly(butyl methacrylate) (PBMA), and Paraloid (R) B-82 acrylic copolymer resins is used as a methanol barrier. In order to implant a proton source in the membrane as homogeneously as possible, the hydrophilic monomers, 2-acrylamido-2-methyl propanesulfonic acid (AMPS), 2-hydroxyethyl methacrylate (HEMA) and a cross-linking agent (poly(ethylene glycol) dimethylacrylate) (PEGDMA) are polymerized after they have been embedded in the TCPB matrix. The embedded polymerization has resulted in an asymmetric membrane structure, in which the hydrophilic network is sandwiched by two outer layers of predominantly hydrophobic TCPB. Measurements are made of properties of the AMPS-containing membranes that are important to fuel cell applications such as water uptake, ion-exchange capacity, proton conductivity, methanol permeability and tensile strength. The highest proton conductivity of the AMPS-containing membrane is about 0.030 S cm-1 at 70 degrees C. The low methanol permeability (10(-8) to 10(-7) cm(2) s(-1)) of the AMPS-containing membranes is their primary advantage for DMFC applications. (c) 2006 Elsevier B.V. All rights reserved.